Textile assistants made from synthetic tanning agents and ammonium compounds



Patented Sept. 27, 1949 MON IUM COMPOUNDS 7 "Eduard Schwagerand Jakob Bindler, Basel, Swit- "zerland; assignors to J. In Geigy A-G., Basel,

Switzerland, a firm 01' Switzerland I No Drawing. Application June 22, 1945, Serial N0. 601,056; In Switzerland July 4, 1944 It has been found that new technically valuable reaction'products are obtained by causing organic compounds containin 'sul'fonic groups and possessing tanning properties to react with quaternary ammonium compounds containing higher molecular aliphatic or cycloaliphatic rad icals. The new products may be used particular? as textile assistants. 'They'po'ssess the surprising properties of being able to slackendown the draw} ing of dyestuffs and thusto guarantee a levelling eifect; simultaneously the new products are especially suitable for the stripping or vat dyestufis. Besides, they can also be usd'ehdressing and finishing agents.

It is known already to combine quaternary ammonium compounds, which contain higher-molecular radicals, with compounds containing sulfonic acid groups. Thus it is known for instance to use vat dye-baths, which contain surface-active compounds capable of dissociation, which compounds are cation=active, such as for instance lauryl pyridinium sulfate, and to add surface-active compounds which are capable of dissociation and are anion-active during thedyeing operation,.such as fat alcohol sulfcnates. The cation-active compound produces. a very extremely retarding efiect' on the yatted dyestufi, which corresponds almost-to a reserving eifect, whereas the anion-active compounds annuls more or less largely the efiect of the former com-: pound. According to thismethod it is possible by mean of addition of the second: assistant to reach any desirable degree of the dyestuli bein initially reserved, so that it is possible' to cause even the complete drawing ofthe dye-bath. Thus the effect or properties of both the auxiliaryproducts neutralize each'other. i

For the same .purpose also similar combinations have been proposed. Thus for instance it is known to prepare vat-dye-baths containing alkali-stable ammonium compounds reacting as a base and being soluble or dispersible' in water, the said ammonium compounds possessingat least one radical of six or'more carbon atoms, and to add protecting colloids or dispersing, agent which can also contain sulfonic acid groups; among the latter compounds may be enumerated for example: castor oil sulfonic acid, sulfonation products of the oleic acid .ethylanilide, etc.-

Furthermore, it is known tofstrip vat dyeings' by 9 Claims (Cl. 260 -451) treating the same with alkaline besides a reducing agent, a quaternary ammonium salt with high-molecular hydrocarbon radicalsand also a purifying agent of the type of the highmolecular' aliphatic sulfonic acids orof sulfuric.

acid esters oflfatt'y alcohols, When working according to this method vat dyestuffs, which other" wise can be stripped onlywith difiiculty, may be stripped easily alsoin the presence of azo dye stufis. V a

Moreover, it' is known to increase the effect of wetting agents containing sulfonic acid groups,

a like dibutylated naphthalene sulfonic acid, by a combination with organic ammonium bases, particularly with those containing an aliphatic radical of 5 toll carbon atoms. However, from these and other publications it could not be derived that new, technically 'valuable products are obtained by combining higher molecular quaternary ammonium compounds with organic compounds containing sulfonic groups, and possessing tanning properties. When compared with similar known combinations the new product show the advantageof a superior efficacy. ,for instance when used as assistants. for dyeing with vat dyestuffs, with acid or direct C1178"; stuffs, etc. In the new combinations the quaternary compounds have surprisingly lost their propcities to mostly precipitate dyestuff, this feature being of importance especially for their use in vat-dyeing and wool-dyeing. a

As quaternary ammonium compounds with higher molecularyaliphaticor cycloaliphatic rad-' icals the known onesmay. be used and partic-ularly the following ones maybe enumerated for example: phenyl-octadecyl-dimethyl ammoniummethyl-sulfate, trimethy-cetyl-ammonium-bromide, \d-i-isopropylbenzyletrimethyl-ammoniumbromide, dodecyl-pyridinium-sulfate, dodecyl-hydroxymethyl-pyridinium-chloride, dodecyl-benzene 0c trimethyl-ammonium-methyl sulfate,

methyl-sulfate of trimethylaminoacet-N-dodecyl-anilide, 4-stearylaminophenyl-trimethylammonium-methyl",- sulfate, stearylaminoethyltrimethyleammoniumemethyl-sulfate and the like. H

As compounds containing sulfon-ic acid groups and having tanning properties, there may be used any condensation products known in the trade 'or by patent literature, such as naphthalene-sm l baths containing,

or unstable to alkalis yield the same good results:

In accordance with the ratios applied the pr perties of the final products will change, this being often very Valuable for the production of special effects. The new products can be made as such and isolated for instance by salting out, by evaporation, etc., but, on the other hand, they can be produced previously with success in the application baths. A

The following examples will illustrate'the present invention, without limiting the same; the parts are by weight, unless otherwise stated.

EXAMPLE 1 20 parts of phenyl-stearyl-dimethyl-ammonium-methyl-sulfate are completely dissolved by stirring in 1600 parts ofwater, the temperature being raised at the end of the operation to about 45-50 C. Then a solution of 240 parts by vol ume of a liquid tanning substance in 2000 parts of water is caused to flow thereinto in a thin jet, the said tanning substance being obtainable by condensation of crude cresol sulfonic acid, urea and formaldehyde according to French Patent 46,179, being a patent of addition to French Patent 660,008, and its solution being maintained at 45-50 C. The new reaction productthus is produced after some time, while a strong-turbidity occurs. Now, 600 parts of sodium chloriderare added, whereby the new compound is completely precipitated. The temperature is increased for a short time to 50 C. and then is cooled down to 20-25 C. The precipitate is filtered by suction and washed with water. After drying at 50 60 C. in vacuo a yellowish-brown powder is obtained which is clearly soluble in water on addition of a base.

EXAMPLE 2 parts of phenyl-stearyl-dimethylammonium-methyl-sulfate are dissolvedin 40 partsof water at 50-60 C.; then 50 parts of a condensa I tion product obtainable from naphthalene sulfonic acid and formaldehyde are introduced under stir ing on the water-bath and heated until a homogeneous viscous solution has been formed.

EXAMPLE 3 A solution of parts of methyl-sulfate of trimethyl-aminoacet-N-dodecylamide in 800 parts by volume is allowed to flow in form of a thin jet into a solution of 120 parts by volume of a syn thetical tanning substance, prepared according to French Patent 723,883 by condensation of dihy droxy diphenyl sulfone with naphthalene-sulfonic acid and formaldehyde, in 1200 parts by volume of water, the said solution being main tained at 50 C. A milky turbidity is produced. On addition of sodium chloride the new product is precipitated. Then it is cooled, filtered and the filter-mass is dried in 'vacuo.

Thus there is obtained a yellowish powder being clearly soluble in water, when adding a base.

A similar final product is also obtained by means of any analogous tanning substance containing sulflte lye.

EXAMPLE 4 10 parts of methyl-sulfate of trimethylaminoacet-N-dodecylanilide are dissolved in 100 Darts by volume of water and combined gradually at C. with an aqueous solution of a synthetical tanning agent obtainable according to French Patent 847,029, i. e. a condensation product from phenol monosulfonic acid and naphthalene monosulfonic acid. While a strong turbidity occurs, the formation of the new product is effected, the latter being precipitated by means of sodium chloride. After the usual Working up a yellowish powder is obtained which is soluble in water on addition of an alkali.

According to the indications made in the above examples also the following compounds may be combined together:

dodecylhydroxymethyl-pyridinium-chloride+tanning substance obtainable according to French patent of addition 45,250, addition to French Patent. 723,883, trimethyh aheptadecylbenzyl) ammonium methyl-sulfate-e. tanning substance according to French patent of addition 46,179, addition to French Patent 660,008, trimethyl-octadecenyl ammonium methyl-sulfate+tanning substance according to. French pat ent of addition 46,179, methyl-:sulfate of trimethyl aminoacet-N-octadecylanilide+tanning substance according to French Patent 46,179 and so on.

Instead of the compounds mentioned in the above examples, also the other compounds enumerated in the introducing part of the specification may be used, whereby reaction products .With similar properties are obtained.

It will be manifest to the skilled inthe art from the above examples,an d more particularlyfrom Examples 1, 2 and 4, that a minimum of two sulfonic acid groups are present for each mol of quaternary ammonium compound used in the reaction.

EXAMPLE 5 A strand of staple fibre is dyed in a dye-bath ratio of 1:30 in the usual manner with 1% of Tinone-chloroviolet RN (Schultz Farbstofftabeh len, 7th edition, vol. 2, page2l3) at '60 C. in hour. If 0.4 or 2 grs. respectively of the reaction products obtainable according to Example 1 or 2 respectively are added per litre of dye-bath, a strong retarding power, a better levelling power and a better dyeing is obtained than with a dyebath containin no assistant. Besides, th leuco dyestuif is dissolved in a much more highly dispersed manner, the vat is almost clear and thus much more stable; the vat contains nearly no vat flower and has, therefore, a less tendency to pro duce precipitates which smear thedyed material and yield uneven dyeings which are not fast to rubbing.

EXAMPLE 6 Stripping power of dyed vat-dyestufis Staple fibres dyed with 2% of Tinone-chloroblue BL (Schultz Farbstofitabellen, 7th edition, vol. 2, page 212) are treated in a bath containing 4 grs. of sodium hydrosulfite and 16 com. of caustic soda dye of 36 B per litre. The stripping effect is relatively small. The same is substan tially increased by adding to the stripping bath per litre thereof 2 grs. of the compound accord- EXAMPLE 7 Retarding power on dyeing with slightly acid dyestuffs Carpet-yarn is dyed in the dye-bath ratio of 1:30 with 2% of Polar-red B concentrated (Schultz Farbstofi'tabellen, 7th edition, vol. 2, page 1'75) under addition of 10% of Glaubers salt and 3% of 30% acetic acid. Then at 60 C. the wool is introduced into the dye-bath supplied with all of the additional products, the mixture being heated to 95 C. and maintained at this temperature for one hour. ,Then it is rinsed and dried. When per litre of dye-bath 2 grs. of a reaction product disclosed in Example 2 are added, there may be observed a strong retarding power, this being in contrast with ordinary dyeings. In contradistinction to the quaternary compounds used alone the new reaction products do not practically influence the shade of the dyeings.

EXAMPLE 8 Retarding power on dyeing with direct dyestufis Staple fibre rags are dyed in the dye-bath ratio of 1:40 with 3% of diphenylcatechine DB (Schultz Farbstofftabellen, 7th edition, vol. 2, page 83) at 95 C. under addition of 30% of Glaubers salt. The retarding power is examined by hanging one staple fibre rag first for 5 minutes in such a manner into the dye-bath that only one half thereof is dipped in, the whole rag being subsequently dyed at 95 C. for 40 minutes. Then it is rinsed and dried. Without addition of a condensation product of the present invention dyeings are produced, the half portion thereof being dyed in an uneven way, that is to say the levelling of the dyeings is unsatisfactory. However, if 2 grs. per litre of a condensation product disclosed in the present specification, for instance of the product obtainable according to Example 2, are added, dyeings of brighter, but distinctly more even shades are obtained.

What we claim is:

1. Process for the manufacture of a Water-soluble textile assistant, which comprises reacting in aqueous medium a synthetic tanning agent containing sulfonic acid groups with a cation-active quaternary ammonium compound containing a hydrocarbon radical selected from the group consisting of aliphatic and araliphatic hydrocarbon radicals containing 12 to 24 carbon atoms, a minimum of two sulfonic acid groups being present for each mol of quaternary ammonium compound, and finally rendering alkaline the obtained product, whereby it is converted into water-soluble form.

2. A process for the manufacture of a Watersoluble textile assistant, which comprises reacting in aqueous medium a synthetic tanning agent containing aromatically bound sulfonic acid groups with a cation-active quaternary ammonium compound containing a hydrocarbon radical selected from the group consisting of aliphatic and araliphatic hydrocarbon radicals containing 12 to 24 carbon atoms, a minimum of two sulfonic acid groups being present for each mol of quaternary ammonium compound, and finally rendering alkaline the obtained product, whereby it is converted into water-soluble form.

3. As a textile assistant, a water-soluble alkalinized reaction product obtained by the process of claim 2.

4. The process according to claim 2, wherein the tanning agent is a condensation product from naphthalene sulfonic acid and formaldehyde, and the quaternary ammonium compound is phenyldimethyl-stearyl-ammonium-methosulfate.

5. As a textile assistant, the water-soluble alkalinized reaction product obtained by the process of claim 4.

6. The process according to claim 2, wherein the tanning agent is a condensation product from cresolsulfonic acid, urea and formaldehyde, and the quaternary ammonium compound is phenyldimethyl-stearyl-ammonium-methosulfate.

'7. As a textile assistant, the water-soluble alkalinized reaction product obtained by the process of claim 6.

8. The process according to claim 2, wherein the tanning agent is a condensation product from phenol-monosulfonic acid and naphthalene monosulfonic acid, and the quaternary ammonium compound is the methosulfate of trimethylaminoacet-N-dodecylanilide.

9. As a textile assistant, the water-soluble alkalinized reaction product obtained by the process of claim 8.

EDUARD SCHWAGER. JAKOB BINDLER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

